CN111004128A - Production process of 3, 5-dichloroaniline - Google Patents
Production process of 3, 5-dichloroaniline Download PDFInfo
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- CN111004128A CN111004128A CN201911234336.3A CN201911234336A CN111004128A CN 111004128 A CN111004128 A CN 111004128A CN 201911234336 A CN201911234336 A CN 201911234336A CN 111004128 A CN111004128 A CN 111004128A
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- dichloroaniline
- pentachloroaniline
- hexachlorobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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Abstract
A3, 5-dichloroaniline production process, under the conditions of certain proportion, temperature, pressure and time, hexachlorobenzene and liquid ammonia carry out ammoniation reaction in an aprotic polar solvent to generate pentachloroaniline and ammonium chloride; separating pentachloroaniline from ammonium chloride and an aprotic polar solvent; the pentachloroaniline is reduced into 3, 5-dichloroaniline under the action of a catalyst. The method for producing 3, 5-dichloroaniline by using hexachlorobenzene as a main raw material increases the outlet of hexachlorobenzene, greatly reduces the cost of raw materials, has the advantages of easily obtained raw materials, short reaction steps, simple process, suitability for industrial production and good market prospect.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a production process of 3, 5-dichloroaniline.
Background
3, 5-Dichloroaniline is an intermediate of dye, pesticide and medicine, is called 3, 5-dichloraniline by English name, CAS626-43-7, is a pure needle-shaped crystal, has the melting point of 51-53 ℃, the boiling point of 259-260 ℃/98.7kPa, is dissolved in ethanol and ether, is insoluble in water, has high toxicity and corrosivity, and is mainly used for manufacturing procymidone, sclerotium, dimetachlone, a bactericide, vinclozolin, iprodione and the like. The compound is also widely used for synthesizing dyes, photochromic materials, pigments, medicines and plant growth promoters. At present, due to the increase of the yield of the agricultural fungicide of the cyclic imide, the intermediate 3, 5-dichloroaniline is in short supply and demand. Therefore, it is of great significance to research simple and economical synthetic methods and industrialize them.
The synthesis method of 3, 5-dichloroaniline mainly includes a mixed dichlorobenzene method, an acetanilide method, a polyhalogenated aniline dehalogenation and hydrogenation method, a 1, 3, 5-trichlorobenzene ammonolysis method, a 2, 6-dichloro-4-nitroaniline method, a Hoffman method of 3, 5-dichlorobenzamide and an o-nitroaniline method. The main processes for producing 3, 5-dichloroaniline at present comprise:
⑴ the process for preparing 3, 5-dichloronitrobenzene from 2, 6-dichloro-4-nitroaniline includes diazotizing, neutralizing, desolventizing, washing with water, distilling, and reducing and distilling to obtain 3, 5-dichloroaniline.
⑵ the process comprises bromizing mixed dichlorobenzene to obtain mixed dichlorobromobenzene, isomerizing to obtain 3, 5-dichlorobromobenzene, ammonolysis, and filtering to obtain the final product, wherein the process comprises selecting cheap and easily-obtained mixed dichlorobenzene as raw material, but the bromination reaction can generate strong acidic hydrogen bromide to pollute environment, and the ammonification reaction needs to be carried out at high temperature, thus the operation is unsafe, and the ammonia water has large pollution to environment, which can not meet the requirement of clean production.
⑶ the 3, 5-dichloronitrobenzene is used as raw material to obtain 3, 5-dichloroaniline by catalytic hydrogenation or hydrochloric acid-iron powder reduction.
CN1690040A discloses a method for preparing 3, 5-dichloroaniline by using 4-chloro-2-nitrotoluene generated in the production of 6-chloro-2-nitrotoluene as a raw material, performing chlorination, rectification and separation to obtain 4, 6-dichloro-o-nitrotoluene, performing oxidation reaction and hydrogenation reduction to obtain 4, 6-dichloroaminobenzoic acid, and performing decarboxylation to obtain the product, namely 3, 5-dichloroaniline, wherein the raw material source is sufficient and low, but the total reaction yield is about 61%.
CN103508901A discloses a method for producing 3, 5-dichloroaniline by using m-nitrochlorobenzene oil as a raw material, adding an organic solvent, performing one-step chlorination to directly produce a pentachloronitrobenzene mixture under the action of a catalyst, and then performing dechlorination reduction reaction under the action of the organic solvent and the catalyst.
CN103102276A discloses a method for preparing 3, 5-dichloroaniline by using 2, 4-dichloroaniline as a raw material and adding an ammonia water catalyst for reaction, wherein the method has the advantages of longer steps, more required equipment and high raw material cost, the price of the intermediate product 3, 5-dichlorobromobenzene is higher than that of the product 3, 5-dichloroaniline, bromine is used in the reaction, the pollution is serious, and the method has no industrial significance.
Disclosure of Invention
The invention aims to provide a production process for producing 3, 5-dichloroaniline, which overcomes the problems of serious environmental pollution, high cost, low content and the like in the existing production of 3, 5-dichloroaniline and provides a novel synthetic method of 3, 5-dichloroaniline.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
⑴ under certain conditions of proportion, temperature, pressure and time, hexachlorobenzene and liquid ammonia are ammoniated in an aprotic polar solvent to generate pentachloroaniline and ammonium chloride;
⑵ separating pentachloroaniline from ammonium chloride and aprotic polar solvent;
⑶ pentachloroaniline is reduced into 3, 5-dichloroaniline under the action of a catalyst.
The aprotic polar solvent described in step ⑴ is N-methylpyrrolidone (NMP) or N, N-Dimethylformamide (DMF).
The ratio in step ⑴ is to set hexachlorobenzene at 1 molar part, liquid ammonia at 5-6 molar parts, and aprotic polar solvent at 8-10 molar parts.
The molar ratio of hexachlorobenzene, liquid ammonia, and aprotic polar solvent described in step ⑴ is preferably 1:5: 9.
The temperature in the step ⑴ is 180-240 ℃, the pressure is 1-4 Mpa, and the time is 1.5-3.5 h.
The temperature in the step ⑴ is preferably 190-230 ℃, the pressure is preferably 1.5-3 Mpa, and the time is preferably 2-3 h.
The separation process of the step ⑵ is that solid ammonium chloride is filtered out by a solid-liquid filtration separation method, and pentachloroaniline is separated from the aprotic polar solvent by decompression rectification.
The catalyst of step ⑶ is a palladium on carbon catalyst.
The mass percentage of palladium in the palladium carbon catalyst is 1-10%.
The mass percentage of palladium in the palladium carbon catalyst is preferably 5%.
The method for producing 3, 5-dichloroaniline by using hexachlorobenzene as a main raw material increases the outlet of hexachlorobenzene, greatly reduces the cost of raw materials, has the advantages of easily obtained raw materials, short reaction steps, simple process, suitability for industrial production and good market prospect.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
N-methylpyrrolidone (NMP) is hereinafter referred to as NMP and N, N-Dimethylformamide (DMF) is hereinafter referred to as DMF.
Example 1
The process flow of the embodiment is as follows:
⑴ mixing hexachlorobenzene with liquid ammonia and NMP in the molar ratio of 1:5:8, and reacting at 180 deg.C and 1.5MPa for 1.5h to obtain pentachloroaniline and ammonium chloride.
⑵ ammonium chloride is removed by filtration, and NMP and pentachloroaniline are separated by rectification under reduced pressure.
⑶ the pentachloroaniline is reduced into 3.5-dichloroaniline under the action of palladium carbon catalyst with the mass percent of palladium of 8%.
Under the conditions, the conversion rate of hexachlorobenzene is larger than or equal to 97 percent, and the yield of 3, 5-dichloroaniline is larger than or equal to 95 percent.
Example 2
The process flow of the embodiment is as follows:
⑴ mixing hexachlorobenzene with liquid ammonia and DMF at the molar ratio of 1:6:8, and reacting at 200 deg.C and 1MPa for 3h to obtain pentachloroaniline and ammonium chloride.
⑵ the ammonium chloride is filtered and removed, and then the DMF and pentachloroaniline are separated by rectification under reduced pressure.
⑶ the pentachloroaniline is reduced into 3.5-dichloroaniline under the action of palladium carbon catalyst with the mass percent of palladium of 4%.
Under the conditions, the conversion rate of hexachlorobenzene is larger than or equal to 96 percent, and the yield of 3, 5-dichloroaniline is larger than or equal to 95 percent.
Example 3
The process flow of the embodiment is as follows:
⑴ mixing hexachlorobenzene with liquid ammonia and NMP in the molar ratio of 1:5.5:9, and reacting at 190 deg.C and 3MPa for 2.5h to obtain pentachloroaniline and ammonium chloride.
⑵ ammonium chloride is removed by filtration, and NMP and pentachloroaniline are separated by rectification under reduced pressure.
⑶ the pentachloroaniline is reduced into 3.5-dichloroaniline under the action of palladium carbon catalyst with the mass percent of palladium of 5%.
Under the conditions, the conversion rate of hexachlorobenzene is larger than or equal to 97.5 percent, and the yield of 3.5-dichloroaniline is larger than or equal to 97.3 percent.
Example 4
The process flow of the embodiment is as follows:
⑴ mixing hexachlorobenzene with liquid ammonia and NMP according to the mol ratio of 1:6:10, reacting for 3.5h at 210 ℃ and 2MPa to generate pentachloroaniline and ammonium chloride.
⑵ ammonium chloride is removed by filtration, and NMP and pentachloroaniline are separated by rectification under reduced pressure.
⑶ the pentachloroaniline is reduced into 3.5-dichloroaniline under the action of palladium carbon catalyst with the mass percent of palladium of 1%.
Under the conditions, the conversion rate of hexachlorobenzene is larger than or equal to 98 percent, and the yield of 3, 5-dichloroaniline is larger than or equal to 94.8 percent.
Example 5
The process flow of the embodiment is as follows:
⑴ mixing hexachlorobenzene with liquid ammonia and DMF at the molar ratio of 1:5:9, and reacting at 240 deg.C and 3.5MPa for 2h to obtain pentachloroaniline and ammonium chloride.
⑵ the ammonium chloride is filtered and removed, and then the DMF and pentachloroaniline are separated by rectification under reduced pressure.
⑶ the pentachloroaniline is reduced into 3, 5-dichloroaniline under the action of palladium carbon catalyst with 10 percent of palladium by mass
Under the conditions, the conversion rate of hexachlorobenzene is larger than or equal to 98.5 percent, and the yield of 3.5-dichloroaniline is larger than or equal to 96 percent.
Example 6
The process flow of the embodiment is as follows:
⑴ mixing hexachlorobenzene with liquid ammonia and NMP in the molar ratio of 1:5.5:8, and reacting at 230 deg.C and 4MPa for 3 hr to obtain pentachloroaniline and ammonium chloride.
⑵ ammonium chloride is removed by filtration, and NMP and pentachloroaniline are separated by rectification under reduced pressure.
⑶ the pentachloroaniline is reduced into 3.5-dichloroaniline under the action of palladium carbon catalyst with the mass percent of palladium of 5%.
Under the conditions, the conversion rate of hexachlorobenzene is larger than or equal to 97.8 percent, and the yield of 3.5-dichloroaniline is larger than or equal to 97.5 percent.
According to the above examples, it can be seen that the conversion of hexachlorobenzene ≧ 98.5% is the highest when hexachlorobenzene is mixed with liquid ammonia and an aprotic polar solvent in a molar ratio of 1:5: 9. The effect of selecting NMP and DMF as the aprotic polar solvent is similar, and NMP is preferable in terms of cost and the like. In examples 3 and 6, a palladium-on-carbon catalyst with 5% by weight of palladium was used, and the ratio of the yield of 3.5-dichloroaniline to the conversion rate of hexachlorobenzene was 99.8% and 99.7%, which are the highest, and the ratio was the yield of reduction of pentachloroaniline to 3.5-dichloroaniline over the catalyst, so the catalyst was preferably a palladium-on-carbon catalyst with 5% by weight of palladium.
Claims (10)
1. The production process of 3, 5-dichloroaniline is characterized by comprising the following steps:
⑴ under certain conditions of proportion, temperature, pressure and time, hexachlorobenzene and liquid ammonia are ammoniated in an aprotic polar solvent to generate pentachloroaniline and ammonium chloride;
⑵ separating pentachloroaniline from ammonium chloride and aprotic polar solvent;
⑶ pentachloroaniline is reduced into 3, 5-dichloroaniline under the action of a catalyst.
2. The process according to claim 1, wherein the aprotic polar solvent used in step ⑴ is N-methylpyrrolidinone (NMP) or N, N-Dimethylformamide (DMF).
3. The process for producing 3, 5-dichloroaniline according to claim 1, wherein the mixing ratio in step ⑴ is 1 mol portion of hexachlorobenzene, 5-6 mol portions of liquid ammonia, and 8-10 mol portions of aprotic polar solvent.
4. The process according to claim 3, wherein the molar ratio of hexachlorobenzene to liquid ammonia to aprotic polar solvent is 1:5: 9.
5. the process for producing 3, 5-dichloroaniline according to claim 1, wherein the temperature in step ⑴ is 180-240 ℃, the pressure is 1-4 Mpa, and the time is 1.5-3.5 hours.
6. The process for producing 3, 5-dichloroaniline according to claim 4, wherein the temperature is 190-230 ℃, the pressure is 1.5-3 Mpa, and the time is 2-3 hours.
7. The process for producing 3, 5-dichloroaniline according to claim 1, wherein the separation in step ⑵ comprises filtering ammonium chloride to remove ammonium chloride, and separating pentachloroaniline from the aprotic polar solvent by rectification under reduced pressure.
8. The process according to claim 1, wherein the catalyst used in step ⑶ is palladium on carbon.
9. The process for producing 3, 5-dichloroaniline according to claim 8, wherein the palladium-carbon catalyst contains 1-10% by weight of palladium.
10. The process according to claim 9, wherein the palladium-on-carbon catalyst comprises about 5% by weight of palladium.
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| CN201911234336.3A CN111004128A (en) | 2019-12-05 | 2019-12-05 | Production process of 3, 5-dichloroaniline |
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| CN201911234336.3A CN111004128A (en) | 2019-12-05 | 2019-12-05 | Production process of 3, 5-dichloroaniline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181089A (en) * | 2021-12-20 | 2022-03-15 | 中建安装集团有限公司 | Method for continuously synthesizing p-nitroaniline |
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| US20140142147A1 (en) * | 2011-07-18 | 2014-05-22 | Georgia State University Research Foundation | Carbocyanines for G-Quadruplex DNA Stabilization and Telomerase Inhibition |
| CN106699571A (en) * | 2016-11-16 | 2017-05-24 | 南京工业大学 | Preparation method of 2,5-dichloroaniline |
| CN106748801A (en) * | 2016-12-28 | 2017-05-31 | 华东师范大学 | A kind of synthetic method of 3,5 dichloroaniline |
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2019
- 2019-12-05 CN CN201911234336.3A patent/CN111004128A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140142147A1 (en) * | 2011-07-18 | 2014-05-22 | Georgia State University Research Foundation | Carbocyanines for G-Quadruplex DNA Stabilization and Telomerase Inhibition |
| CN106699571A (en) * | 2016-11-16 | 2017-05-24 | 南京工业大学 | Preparation method of 2,5-dichloroaniline |
| CN106748801A (en) * | 2016-12-28 | 2017-05-31 | 华东师范大学 | A kind of synthetic method of 3,5 dichloroaniline |
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| VLADIMIRI.RODIONOV等: "Selective mono-and diamination of some polyhalogenbenzenes in anhydrous ammonia", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181089A (en) * | 2021-12-20 | 2022-03-15 | 中建安装集团有限公司 | Method for continuously synthesizing p-nitroaniline |
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